Anthracene dye and process of making same.



' anthraquinone and'l-amino 7 halogen an- UNITED STATES PATENT OFFICE.

- MAX HENRY ISLER, or MANNHEIM, HUGO woLFF; OF'LtlfiWIGSEAFENON-THE-RHINE, AND FILIP KACER, or MANNHEIM, GERMANY, ASSIGNORS TOBADISCHE ANILIN & SODA ,FABRIK, or LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, ACORPORATION OF GERMANY.

. AN'IIHRACENE DYE AND rniiensson Max ne same.

Specification of Letters Patent. T V

Patented July 27, 1909.

Application filed March 25, 1909. Serial No. 486,673.-

To. all whom it may concern:

Be it known that we, MAX HENRY -ISLER,. chemist, and HUGO l VOLFF andFILIP KAER, doctors of philosophy and chemists, respectively a citizenof the Swiss Republic, a subj ect of the Grand Duke of Baden, and asubject of the'K'ing of Prussia, residing the second-named atLudwigshafen-on-the-Rhine and the others at Mannheim, all in Germany,have invented new and useful Improvements in Anthracene Dyes andMakingthe Same, of which the following is a specification.

In the specification of German Patent No. 162,824 is described theproduction of dianthraquinone imids by condensing l-halogenanthraquinone with l amino anthraquinone, orwith Q-amino-anthraquinone,or with derivatives of l-amino-anthraquinone,

and in the specification of Letters Patent No.

814,137 is described the condensation of 2- ,chlonanthraquinone withl-amino-anthraquinone.

' We have now discovered that compounds possessing properties differentfrom those of the aforementioned products and being vat coloring mattersof excellent fastness, can be obtained by condensing 1 aminoanthraquinone with a derivative of a 2-halogen-anthraqninone compound,or by condensing a derivative of a l-amino-anthraquinone compound with a2-halogenanthraquinone,'or with a derivative thereof. In each case thereis obtained a substituted alpha-betadianthraquinone imid containing onlytwo anthraquinone residues.

As examples of the derivatives ofl-aminoanthraquinone and of2-halogen-anthraquinone which can be used for the purposes of ourinvention, we mention'the alkylamino" and aryl-aminoderivatives, theacyl-amino derivatives, .the-alkyl-oxy and aryl-oxy derivatives,'andath0se obtainedwhen an extra ring is joined to the anthraquinone group,for instance amino anthraquinone quinolin. Derivatives such asl-amino-G-halogeilthraquinone, as wellas diamino-anthraquinone, and'dihalo en-anthraquinones, which,

by permitting urthgr condensation, give rise to compounds containingmorethan two anthraquinone' residues and also derivatives which do notcontain the two ketone groups intact, are not to be used for thepurposes of this invention.

Thefollowing are examples of how our einvention can be carried intopractical effect, but our invention is not confined to these examples.The parts are by weight.

Example 1: Boil together for from five, to seven, hours, fourteen partsof l-methylamino-(i-chlor-anthraquinone (obtainable by boiling1-nitro-G-chlor-anthraquinone with a none (obtainable by heating1-amino-6-chloranthraquinone with a solution of methylamin underpressure and at a temperature of one hundred and seventy degreescentigrade), and twenty-four parts of 2-chloranthraquinone as describedin the foregoing -Example 1. 'The corresponding coloring matter can beobtained by'employing I-ami- 110-7 -methyl-aminoanthraqunione instead of1-amino-6-methyl-a1nino-anthraqninone.

' Example 3: Condense together twenty parts of1-an1ino6-methyl-amino-anthraqninone and twenty parts of2-chlor-5-mcthylamino-anthraquinone (obtainable by boiling5-nitro-2-chlor-anthraquinone with a solution of methyl-amin inpyridin), as described in the foregoing Example 1. The correspondingcoloring matters can be obtained by employing1-21mino-7-methyl-amino-anthraqui none instead of1-:iminofi-methyl-amino-anthraquinone, or by employing 2-chlor-S-nicthyl-amino-anthraquinone instead of 2-c'hlor-5-methy1-aminosanthraqulnone.

Example 4: Condense-together seventeen parts of2-chlor-5-toluido=anthraqiiinone (obtainableby boiling 2-chlor-5-nitro-anthraquinone with para-toluldin) and eleven parts ofl-amino-anthraquinone as" described in the foregoing Example 1. Thecorresponding coloring matters can be obtained by employing 2-chlor-8tolu1do-anthraqu1none lnstead of 2-chlor-5-toluido-anthraquinone, or byem i0 caustic potash .in methyl alcohol), as described in the foregoingExample 1. The corresponding coloring matters can be obtained byemploying 2-chlor-5-methoxy-anthraquinone, or2-chlor-fi-oxy-anthraquinone,

or -2-chlor-S-oxy-anthraquinone, or the corresponding phenoxyderivatives, instead of 2-chlor-S-methoxy-anthraquinone.

Example 6: Condense together fifteen parts of2-chlor-5-nitro-anthraquinone (ob.-

tainable by replacing by chlorin the sulfonic acid group in5-nitro-anthraquinone-Q-sulfonic acid), and eleven and two-fifths partsof l-amino-anthraquinone as described in the foregoing Example 1.Thccorrcsponding coloring matter can be obtained by employing2-chlor,-8-11itroranthraquinone instead of2-chlor-S-nitro-anthraquinone.

Example 7: Condense -together fifteen parts of 1-amino-anthraquinone andtwenty and one-tenth parts of 2-chl0r-8-acetyl-amino-anthraquinone(obtainable by acetylating 2-chlor-S-amino-anthraquinone) as describedin the foregoing Example 1.

Exam le 8; Condense together, as described in the foregoing Example 1,eight parts of 'l-amino-anthraquinone and ten parts of the productobtained by heating 1- acetyl amino 7 chlor anthraquinone withphosphorus oxychlorid by the process described in the specification ofLetters Patent No. 863,401. The corresponding coloring matter can beobtained by employing the product obtainable in a similar manner froml-acetyl-amino-(t-chlor-anthraquinone.

Example S): Condensc together twelve parts ofamino-anthraquinone-2.3-quinolin (obtaiuableby the nitration andsubsequent reduction .of anthraquinone 2.3-quinolin), and thirteen andone-fifth parts of 2-chlor- S-acetyl-amino-anthraquinone as described inthe foregoing Example 1. The col-re sponding coloring matters can beobtained;

by employing iZ-chlor-antln'aquinone, or 2- chlor-5-nitro-anthraquinone,or 2-chlor-fwnitro-anthraquinone, instead of Q-chlor-S-acetyl-amino-anthraquinone.

Example 10: Condense together twelve parts ofamino-antlnnquirfone-Z.l-quiuolin (obtainable by the nitration andsubsequent reduction of anthraquinone-2.1-quinolin), and thirteen andone-fifth parts of Q-chlor- 5-acetyl-amino-antln'aquinone, as describedin the foregoing Example 1. The corresponding coloring matters can beobtained by employing the isomeric amino-anthraquinone-1.2-quinolin, or5-amino-2.3-anthraquinone-quinolin, instead of amino-antlnraquinone 2.1quinolin.

In the foregoing Examples 9 and 10 the nitrogen atom of the pyridin ringis attached to the first-mentioned carbon atom of the anthraquinoneresidue.

In the foregoing examples the copper oxid can be replaced by coppersalts, or by metallic copper, and, instead of sodium carbonate, otheragent capable of fixing hydrochloric acid can beused, for instancesodium acetate, potassium carbonate, or calcium hydrate, and thenitrobenzene can be replaced by naphthalene, or other indiflere'ntsolvent of high boiling point. Y

The following table states some of the properties of the coloringmatters produced according to the foregoing examples Solution iniggggggg gggfig 2 2%; Dyes cotton irom a hydroibregoing. Concentrated sulfuricConcentrated sulfuric Concentrated sulfuric Sulfite v acid. acid+boricacid. acid-i-boric acid, hot.

Example. 1 Bottle-green. Violet-blue. Violet. Brownish red-Bottle-green. Violet-blue. Violet. Brownish red.

. Brown. Brown-violet. Violet. Bordeaux. Olive, (fluorescent.)Blue-violet. Red-violet. Bordeaux. Brown-yellow. Brown-red. Dull red;Brick red. Dull bottle-green. Unchanged. Blue-violet. Dull red.

Bottle-green. Blue-violet. Violet. Brick red. Red-brown. Unchanged.Violet-brown. Brick red. Dulkblue-green. Unchanged. Violet. Brick red. 1Brownish olive. Unchanged. Blue. Violet-brown.

Now what we claim is:

I 1. The process of producing coloring matter of the anthracene seriesbeing substituted alpha beta dianthraquinone imids by condensing al-amino-anthraquinone body with a 2 -ha1ogen anthra uinone body both ofsuch anthraquinone two ketonic groups intact and oneat least odiescontaining theof such anthraquinone bodies beingsubstituted by asubstituent which is incapable of reacting on the other anthraqumonebody employed.

2. The process'of producing coloring matter of the anthracene series bycondensing 1-methyl-amino-fi-chlor-anthraquinone withl-amino-anthraquinone.

3. As new articles of manufacture the coloring matters of the anthraceneseries being substituted alpha-beta-dianthraquinone imids which can beobtained by condensing a l-amino anthraquinone body with a2-halogen-anthraquinone body both of such anthraquinone bodiescontaining the two ket-onic groups intact and one at least of suchanthraquinone bodies being substituted by a substituent Which'isincapable of reacting on the other anthraquinone body employed, whichcoloring matters yield from red-brown to green solutions in'coldconcentrated sulfuric acid, from brown-red to Violet-blue solutions incold concentrated sulfuric acid to which boric acid has been added, fromred to blue solutions in hot concentrated sulfuric acid to which boricacid hasbeen added, and

which'dye cotton from a hydrosulfite Vat yielding red to violet-brownshades.

4. As a new article of manufacture the ter yields a bottle greensolution in-cold sulfuric acid, a violet-blue solution in coldconcentrated sulfuric acid to which boric acid has been added, a violetsolution in hot concentrated sulfuric acid to which boric 7 acid hasbeen added, and-which dyes cotton from a hydrosulfite Vat yieldingbrownish red shades.

In testimony whereof we have hereunto set our hands in the presence oftwo-subscribing witnesses.

MAX HENRY ISLER. HUGO WOLFF. FILIP KACER.

Witnesses:

J. ALEC. LLOYD, J 0s. H. LEUTE.

